CN101065443A - Fluorine-containing treatment composition - Google Patents
Fluorine-containing treatment composition Download PDFInfo
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- CN101065443A CN101065443A CNA2005800371778A CN200580037177A CN101065443A CN 101065443 A CN101065443 A CN 101065443A CN A2005800371778 A CNA2005800371778 A CN A2005800371778A CN 200580037177 A CN200580037177 A CN 200580037177A CN 101065443 A CN101065443 A CN 101065443A
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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Abstract
Disclosed is a composition containing a fluorine-containing urethane compound (A) and a fluorine-containing polymer (B) having a repeating unit derived from a fluorine-containing monomer represented by the following formula (I): CH2=C(-X)-C(=O)-A-Rf (I) (wherein X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX<1>X<2> group (wherein X<1> and X<2> respectively represent a hydrogen atom, a fluorine atom or a chlorine atom), a cyano group, a straight or branched chain fluoroalkyl group having 1-20 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group; A represents a divalent group; and Rf represents a straight or branched chain perfluoroalkyl group having 1-6 carbon atoms).
Description
Technical field
The present invention relates to give the agent composition, particularly surface treatment composition of the water-repellancy of the parts of fibre product (for example carpet), paper, non-woven fabrics, stone material, static filter, dust respirator, fuel cell with excellence, grease proofness, didirtresistance.
Background technology
In the past, the scheme that proposes for agent composition had the combination of fluorine-containing urethane compound and fluoropolymer.For example, US2003/0204015 A1 discloses a kind of agent composition, and it contains fluorine-containing urethane compound and fluorine-containing (methyl) acrylate/polyoxyalkylene (methyl) acrylate copolymer.Yet there is the inadequate shortcoming of water and oil-resistant in this agent composition.
By nearest result of study (EPA reports " PRELIMINARY RISKASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATEDWITH EXPOSURE TO PERFLUOROOCTANOIC AICD AND ITS SALTS " (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)) etc.; (Perfluorocaprylic Acid: perfluorooctanoic acid) worry of the load that brings to environment has become clearly, and the scientific research to PFOA is strengthened in EPA on April 14th, 2003 (the U.S. environment protection Room) issue to PFOA.
On the other hand, Federal Register (FR Vol.68, No.73/April 16,2003[FRL-7303-8]) (http://www.epa.gov/opptintr/pfoa/pfoafr.pdf) and EPAEnvironmental News FOR RELEASE:MONDAY APRIL 14,2003; EPAINTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICALPROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) and EPAOPPT FACT SHEET April 14,2003 (http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf) have announced that " telomer " might be by decomposing or metabolism generation PFOA.In addition, announced also that " telomer " is used to fire foam; Care article and Cleaning preparations; Be set at the most of goods that contain waterproof and oilproof lining and antifouling processing lining of tilting blanket, textiles, paper, leather.
Summary of the invention
The object of the present invention is to provide the agent composition with water-repellancy, grease proofness and the didirtresistance of excellence such as the base material of can giving fibre product.
The invention provides a kind of composition, it contains (A) and (B):
(A) fluorine-containing urethane compound;
(B) have fluoropolymer by the fluorochemical monomer institute repeat units derived of formula (I) expression,
CH
2＝C(-X)-C(＝O)-A-Rf (I)
In the formula (I), X is fluorine atom, chlorine atom, bromine atoms, iodine atom, CFX
1X
2Group (X
1And X
2Be hydrogen atom, fluorine atom or chlorine atom), cyano group, carbonatoms is 1～20 a straight chain shape or a chain fluoro-alkyl, the benzyl that replaces or do not have replacement, replace or do not have the phenyl of replacement;
A is-O-Y
1-(wherein, Y
1Be carbonatoms be 1～10 aliphatic group, carbonatoms be 6～10 aromatic group or cyclic aliphatic group ,-CH
2CH
2N (R
1) SO
2-(CH
2CH
2)
a-group (R
1Be that carbonatoms is 1～4 alkyl, a is 0 or 1) or-CH
2CH (OR
11) CH
2-group (R
11Be hydrogen atom or ethanoyl)) or-Y
2-[(CH
2)
m-Z-]
p-(CH
2)
n-(wherein, Y
2For-O-or-NH-, Z is-S-or-SO
2-, m is 1～10, n is 0～10, p is 0 or 1);
Rf is that carbonatoms is 1～6 a straight chain shape or a chain perfluoroalkyl.
Agent composition of the present invention can be given the water and oil-resistant and the didirtresistance of base material excellence.
Embodiment
Agent composition of the present invention is by containing fluorine-containing urethane compound (A) and fluoropolymer (B) forms.Agent composition can also contain silicon-containing compound (C) except containing fluorine-containing urethane compound (A) and fluoropolymer (B).Agent composition can also contain liquid medium (for example water and/or organic solvent) and tensio-active agent in case of necessity.
Fluorine-containing urethane compound (A) generally represents with following formula,
(Rf’-O-(C＝O)-NH)
aI(NH-(C＝O)-O-R’)
b
[in the formula, each Rf ' is identical or different, is any monovalent organic radical group of containing at least 1 fluorine atom; I removes the organic group that all isocyanate group obtain (a+b) valency from the isocyanate compound with (a+b) individual isocyanate group; Each R ' is identical or different, is any monovalent organic radical group of not contain fluorine atoms; A is 1～15 integer, and b is 0～14 integer, and the summation of a and b is 1～15 integer.]。
In fluorine-containing urethane compound (A), Rf ' can be the group of representing with following formula,
Rf-A
1-Z-X
1-
[in the formula, Rf is that carbonatoms is 1～6 perfluoroalkyl; A
1Be that directly combination or carbonatoms are 1～21 divalent organic group; Z be direct combination ,-S-or-SO
2-; X
1Be that direct combination or the carbonatoms that has at least 1 hydroxyl or do not have a hydroxyl are 1～5 a straight chain shape or a chain divalent aliphatic group.]。
In fluorine-containing urethane compound (A), the example of R ' is the group of following chemical formulation,
H-(O)
s-(CH
2)
t-
(wherein, s is 0 or 1, and t is 1～5 number.)、
-(A
11-O)
p-A
12
(wherein, A
11Be that carbonatoms is 2～5 alkyl, A
12Be that hydrogen atom or carbonatoms are 1～5 alkyl, p is 0～20.) and
-((ClCH
2-)X
2O)
a-R
1
(wherein, X
2Be that carbonatoms is 2～5 a straight chain shape or chain 3 a valency aliphatic group, R
1Be that hydrogen atom or carbonatoms are 1～10 alkyl, a is 1～20 number.)。
Fluorine-containing urethane compound (A) can be the compound of for example formula (1) expression,
[Rf-A
1-Z-X
1-OC(＝O)NH-]
mI[-NHC(＝O)O-Y
1]
n[-NHC(＝O)O-((ClCH
2-)X
2O)
a-R
1]
k (1)
In the formula (1), I removes isocyanate group and the group that obtains from polyisocyanate compounds; Rf is that carbonatoms is 1～6 perfluoroalkyl; A
1Be that directly combination or carbonatoms are 1～21 divalent organic group; Z be direct combination ,-S-or-SO
2-; X
1Be that direct combination or the carbonatoms that has at least 1 hydroxyl or do not have a hydroxyl are 1～5 a straight chain shape or a chain divalent aliphatic group; X
2Be that carbonatoms is 2～5 a straight chain shape or chain 3 a valency aliphatic group; Y
1It is the 1 valency organic group that has hydroxyl or do not have hydroxyl; R
1Be that hydrogen atom or carbonatoms are 1～10 alkyl; A is 1～20 number; M is 1～15 number; N and k are 0～14 numbers; The summation of m and n and k is 2～15 number.
In formula (1), I removes isocyanate group and the group that obtains from polyisocyanate compounds.Polyisocyanate compounds is the compound with at least 2 isocyanate group.Polyisocyanate compounds can be the derivative of fatty family polymeric polyisocyanate, fragrant family polymeric polyisocyanate, these polymeric polyisocyanates.
The example of the particularly fatty family vulcabond of fat family polymeric polyisocyanate is hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenation of benzene dimethylene diisocyanate, hydrogenation dicyclohexyl methane diisocyanate.The example of the particularly fragrant family vulcabond of fragrance family polymeric polyisocyanate is benzylidene vulcabond, diphenylmethanediisocyanate (MDI), tolidine vulcabond, naphthalene diisocyanate.
Polyisocyanate compounds is preferably the isocyanic ester (the particularly adducts of the tripolymer of vulcabond or polyvalent alcohol and vulcabond) of vulcabond, polymeric MDI (diphenylmethanediisocyanate), modification.
ウ レ ト ニ ミ Application), the acylurea vulcabond example of modified isocyanate is the imine modified vulcabond of urethane-modified vulcabond, allophanate-modified vulcabond, biuret modified vulcabond, isocyanurate-modified vulcabond, the vulcabond of carbodiimide modified, a urea (urea imines:.
In formula (1), Rf is that carbonatoms is 1～6 perfluoroalkyl.The carbonatoms of Rf can be for example 1～5, particularly can be 1～4.The example of Rf group is-CF
3,-CF
2CF
3,-CF
2CF
2CF
3,-CF (CF
3)
2,-CF
2CF
2CF
2CF
3,-CF
2CF (CF
3)
2,-C (CF
3)
3,-(CF
2)
4CF
3,-(CF
2)
2CF (CF
3)
2,-CF
2C (CF
3)
3,-CF (CF
3) CF
2CF
2CF
3,-(CF
2)
5CF
3,-(CF
2)
3CF (CF
3)
2Deng.
In formula (1), A
1Be that directly combination or carbonatoms are 1～21 divalent organic group.A
1Group can be for example-(CH
2)
p-,-CONR
11-R
12-,-CH
2C (OH) HCH
2-,-CH
2C (OCOR
13) HCH
2-or-O-Ar-CH
2-[in the formula, R
11Be that hydrogen or carbonatoms are 1～10 alkyl, R
12Be that carbonatoms is 1～10 alkylidene group, R
13Be hydrogen or methyl, Ar has substituting group or does not have substituent arylidene (carbonatoms for example is 6～20), and p is 1～10 integer.]。
A
1Particularly can be 1～5 alkylidene group for carbonatoms.
X
1Be that direct combination or carbonatoms are that 1～5 a straight chain shape or chain divalent aliphatic group or the carbonatoms with at least 1 hydroxyl are 1～5 a straight chain shape or a chain divalent aliphatic group.X
1It can be the alkylidene group that does not have the alkylidene group of hydroxyl or have 1,2 or 3 hydroxyl.X
1The example of group is (i) from by-CH
2-,-CH
2CH
2-,-CH
2CH
2CH
2-,-CH
2CH
2CH
2CH
2-,-CH
2CH
2CH
2CH
2CH
2-,-C (CH
3) H-,-C (CH
3) H-CH
2-,-CH
2-C (CH
3) H-,-CH
2-C (CH
3) H-CH
2-,-C (CH
3) H-CH
2-CH
2-,-C (CH
3) H-C (CH
3) H-,-CH
2-C (CH
3)
2-CH
2-,-C (CH
3) H-C (CH
3) H-CH
2-and-C (CH
3) H-CH
2-C (CH
3) alkylidene group selected in the group formed of H-; And (ii) from by-C (OH) H-,-C (OH) HCH
2-,-CH
2C (OH) H-,-C (OH) HC (OH) H-,-C (OH) HCH
2CH
2-,-CH
2C (OH) HCH
2-,-CH
2CH
2C (OH) H-,-C (OH) HC (OH) HCH
2-,-C (OH) HCH
2C (OH) H-,-CH
2C (OH) HC (OH) H-,-CH
2C (OH)
2CH
2-and-the alkylidene group selected in the group that C (OH) HC (OH) HC (OH) H-forms with hydroxyl.
In the formula (1)-A
1-Z-X
1-group plays a role as spacer.As the object lesson of spacer, for example, can enumerate following group,
-S-(CH
2)
2-
-S-(CH
2)
3-
-SO
2-(CH
2)
2-
-SO
2-(CH
2)
3-
-(CH
2)
2-S-(CH
2)
2-
-(CH
2)
2-S-(CH
2)
3-
-(CH
2)
2-SO
2-(CH
2)
2-
-(CH
2)
2-SO
2-(CH
2)
3-
-S-CH
2C(OH)HCH
2-
-SO
2-CH
2C(OH)HCH
2-
-(CH
2)
2-S-CH
2C(OH)HCH
2-
-(CH
2)
2-SO
2-CH
2C(OH)HCH
2-
Perhaps ,-A
1-Z-X
1-group also can be direct combination.Y
1It is the 1 valency organic group that has hydroxyl or do not have hydroxyl.For example, Y
1Represent with following formula.
H-(O)
s-(CH
2)
t-
(s is 0 or 1, and t is 1～5 number.)
Y
1Example be CH
3-, H (CH
2)
2-, H (CH
2)
3-, HO-CH
2-, HO-(CH
2)
2-, HO-(CH
2)
3-.
For example, Y
1Can be-(A
11-O)
p-A
12(wherein, A
11Be that carbonatoms is 2～5 alkyl, A
12Be that hydrogen atom or carbonatoms are 1～5 alkyl, p is 0～20).P can be 1～15, for example is 2～10.
X
2Be that carbonatoms is 2～5 a straight chain shape or chain 3 a valency aliphatic group.X
2Example be following group.
＞CHCH
2-(-CH
2CH＜)、＞CHCH
2CH
2-(-CH
2CH
2CH＜)、
＞CHCH
2CH
2CH
2-(-CH
2CH
2CH
2CH＜)、
＞CHCH
2CH
2CH
2CH
2-(-CH
2CH
2CH
2CH
2CH＜。
R
1Be that hydrogen atom or carbonatoms are 1～10 alkyl.R as alkyl
1Example be methyl, ethyl, propyl group.
A is 1～20 number.A can be for example 2～15, especially can be 2～10.
M is 1～15 number.M can be for example 2～10, especially can be 2～3.
N and k are 0～14 number.N and k can be for example 0～10, especially can be 1～8.
The summation of m and n and k is 2～15 number.The summation of m and n and k can be for example 2～10, especially can be 2～3.
Fluorine-containing urethane compound of the present invention can be the compound of formula (2) or formula (3) expression.
[Rf-A
1-Z-X
1-OC(＝O)NH-]
mI[-NHC(＝O)O-Y
1]
n (2)
In the formula (2), I removes isocyanate group and the group that obtains from polyisocyanate compounds; Rf is that carbonatoms is 1～21 perfluoroalkyl; A
1Be that directly combination or carbonatoms are 1～21 divalent organic group; Z be direct combination ,-S-or-SO
2-; X
1Be that direct combination or the carbonatoms that has at least 1 hydroxyl or do not have a hydroxyl are 1～5 a straight chain shape or a chain divalent aliphatic group; Y
1It is the 1 valency organic group that has hydroxyl or do not have hydroxyl; M is 1～15 number; N is 0～14 number; The summation of m and n is 2～15 number.
[Rf-A
1-Z-X
1-OC(＝O)NH-]
mI (3)
In the formula (3), I removes isocyanate group and the group that obtains from polyisocyanate compounds; Rf is that carbonatoms is 1～21 perfluoroalkyl; A
1Be that directly combination or carbonatoms are 1～21 divalent organic group; Z be direct combination ,-S-or-SO
2-; X
1Be that direct combination or the carbonatoms that has at least 1 hydroxyl or do not have a hydroxyl are 1～5 a straight chain shape or a chain divalent aliphatic group; M is 2～15 number.
The object lesson of fluorine-containing urethane compound of the present invention (A) is as follows.
Compound group 1
Compound group 2
Compound group 3
Compound group 4
Compound group 5
Compound group 6
Compound group 7
Compound group 8
(Rf in the above-mentioned chemical formula, Y
1With a and above-mentioned equivalent in meaning.)
The chloride ether alcohol reaction that the pure and mild formula that fluorine-containing alcohol that fluorine-containing urethane compound of the present invention (A) for example can be by making polyisocyanate compounds and formula (i) expression and the formula that according to circumstances exists are (ii) represented is (iii) represented obtains.
Rf-A
1-Z-X
1-OH (i)
HO-Y
1 (ii)
HO-((ClCH
2-)X
2O)
a-R
1 (iii)
(Rf in the above-mentioned formula, A
1, Z, X
1, X
2, Y
1, R
1With a and above-mentioned equivalent in meaning.)
In this reaction, the isocyanate group in the polyisocyanate compounds with respect to 1 mole, fluorine-containing alcohol (i) and alcohol (ii) are preferably 0.5～2.0 with chloride ether alcohol total mole number (iii), are preferably 0.8 mole～1.5 moles especially.Alcohol (iii) is that can use also can obsolete composition with chloride ether alcohol (ii).This reaction was preferably carried out 0.1 hour～10 hours in 0 ℃～150 ℃ temperature under the condition that solvent exists.Solvent is for being organic solvent inert to isocyanic ester.The example of solvent is hydrocarbon, ketone, halohydrocarbon (for example chloride hydrocarbon).With respect to 100 weight part reactants, the amount of solvent can be 20 weight parts～500 weight parts, for example is 100 weight parts～300 weight parts.
During reaction, preferably use catalyzer.The example of catalyzer is amine (for example monoamine, diamines, triamine, hydramine, ether amine), organo-metallic (for example organic acid metal-salt (di-n-butyltin dilaurate of can giving an example)).With respect to 100 weight part reactants, the amount of catalyzer can be 0.001 weight part～0.5 weight part, for example is 0.01 weight part～0.3 weight part.
Fluorine-containing alcohol (i) (Z is the compound of-S-) for example can be by making Rf-A
1-I (iodide) and HS-X
1-OH reacts and obtains.Can by with superoxide etc. with Z in the fluorine-containing alcohol (i) of-S--the S-oxidation to be to change into-SO
2-obtain Z and be-SO
2-fluorine-containing alcohol (i).
Alcohol (ii) can be monohydroxy-alcohol, also can be polynary (for example 2 yuan～5 yuan) alcohol.Alcohol example (ii) is fatty alcohol, aromatic alcohols.Alcohol object lesson (ii) is ethanol, propyl alcohol, two tripropylene glycols, TriMethylolPropane(TMP), tetramethylolmethane, phenol, hydroxytoluene.
Chloride ether alcohol (iii) for example can obtain by the chloride cyclic ether compound polymerization that following formula is represented.The example of chloride cyclic ether compound is an Epicholorohydrin.
Compound group 9
(the X in the formula
2With above-mentioned equivalent in meaning.)
Fluorine-containing urethane compound (A) can be the mixture of solution or emulsion form after just making.
The mixture of solution-type contains fluorine-containing urethane compound and solvent.The example of the solvent in the solution-type mixture (particularly organic solvent) is hydrocarbon, ketone, halohydrocarbon (for example chloro-hydrocarbons), alcohol (for example dibasic alcohol).The object lesson of organic solvent can be enumerated acetone, chloroform, HCHC225, Virahol, pentane, hexane, heptane, octane, hexanaphthene, benzene,toluene,xylene, sherwood oil, tetrahydrofuran (THF), 1,4-diox, butanone, methyl iso-butyl ketone (MIBK), ethyl acetate, butylacetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trieline, zellon, C2Cl4F2, Refrigerant R 113 etc.
The mixture of emulsion-type contains fluorine-containing urethane compound, emulsifying agent and water.The mixture of emulsion-type can also contain water-miscible organic solvent, particularly dissolves the water-miscible organic solvent of fluorine-containing urethane compound.As water-miscible organic solvent, can enumerate acetone, butanone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol etc., with respect to the water of 100 weight parts, can use 1 weight part～50 weight parts, the water-miscible organic solvent of 10 weight parts～40 weight parts for example.Emulsifying agent can be any one emulsifying agent of nonionic, ionic (for example cationic, anionic property, both sexes).
In mixture, the amount of fluorine-containing urethane compound can be 0.1 weight %～70 weight %, for example is 5 weight %～30 weight %.In the mixture of emulsion-type, fluorine-containing urethane compound with respect to 100 weight parts, the amount of emulsifying agent can be 0.1 weight part～30 weight parts, 2 weight parts～10 weight parts for example, the amount of water can be 30 weight parts～95 weight parts, 70 weight parts～95 weight parts for example, and the amount of organic solvent can be 0 weight part～200 weight parts, particularly 10 weight parts～200 weight parts, 50 weight parts～100 weight parts for example.
Composition of the present invention contains fluoropolymer (B).
Fluoropolymer (B) has the fluorochemical monomer institute repeat units derived (B-1) by formula (I) expression.
CH
2＝C(-X)-C(＝O)-A-Rf (I)
In the formula (I), X is fluorine atom, chlorine atom, bromine atoms, iodine atom, CFX
1X
2Group (X
1And X
2Be hydrogen atom, fluorine atom or chlorine atom), cyano group, carbonatoms is 1～20 a straight chain shape or a chain fluoro-alkyl, the benzyl that replaces or do not have replacement, replace or do not have the phenyl of replacement; A is-O-Y
1-(wherein, Y
1Be carbonatoms be 1～10 aliphatic group, carbonatoms be 6～10 aromatic group or cyclic aliphatic group ,-CH
2CH
2N (R
1) SO
2-(CH
2CH
2)
a-group (R
1Be that carbonatoms is 1～4 alkyl, a is 0 or 1) or-CH
2CH (OR
11) CH
2-group (R
11Be hydrogen atom or ethanoyl)) or-Y
2-[(CH
2)
m-Z-]
p-(CH
2)
n-(wherein, Y
2For-O-or-NH-; Z is-S-or-SO
2-; M is 1～10, and n is 0～10, and p is 0 or 1); Rf is that carbonatoms is 1～6 a straight chain shape or a chain perfluoroalkyl.
Fluoropolymer (B) can also have by the monomer institute repeat units derived (B-2) of contain fluorine atoms not.
Fluoropolymer (B) can be by have above-mentioned repeating unit (B-1), by the monomer institute repeat units derived (B-2) of contain fluorine atoms not and the fluoropolymer that exists as required, form by cross-linkable monomer institute repeat units derived (B-3).
Fluoropolymer (B) can be to contain the fluorochemical monomer (a) of the formula (I) that the α position replaced by the X group, the multipolymer that forms of the monomer of contain fluorine atoms (b) and the cross-linkable monomer (c) that according to circumstances exists not.
Repeating unit (B-1) is to be derived by the fluorochemical monomer (a) of formula (I) to obtain.In formula (I), the Rf group is preferably perfluoroalkyl.The carbonatoms of Rf group is 1～6, for example be 1～5, especially be 1～4.
A preferably-O-Y
1-(wherein, Y
1Be carbonatoms be 1～10 aliphatic group, carbonatoms be 6～10 aromatic group or cyclic aliphatic group ,-CH
2CH
2N (R
1) SO
2-(CH
2CH
2)
a-group (R
1Be that carbonatoms is 1～4 alkyl, a is 0 or 1) or-CH
2CH (OR
11)-CH
2-group (R
11Be hydrogen atom or ethanoyl)) or-Y
2-[(CH
2)
m-Z-]
p-(CH
2)
n-(wherein, Y
2For-O-or-NH-, Z is-S-or-SO
2-, m is 1～10, n is 0～10, p is 0 or 1).Aliphatic group is preferably alkylidene group (especially carbonatoms is 1～4, for example is 1 or 2).Aromatic group and cyclic aliphatic group can be substituted also and can not be substituted.M and n are preferably 2 or 3.
The example of fluorochemical monomer (a) is as follows.
Compound group 10
Compound group 11
Compound group 12
Compound group 13
CH
2＝C(-F)-C(＝O)-O-(CH
2)
2-S-Rf
CH
2＝C(-F)-C(＝O)-O-(CH
2)
2-S-(CH)-Rf
CH
2＝C(-F)-C(＝O)-O-(CH
2)
2-SO
2-Rf
CH
2＝C(-F)-C(＝O)-O-(CH
2)
2-SO
2-(CH
2)
2-Rf
CH
2＝C(-F)-C(＝O)-NH-(CH
2)
2-Rf
CH
2＝C(-Cl)-C(＝O)-O-(CH
2)
2-S-Rf
CH
2＝C(-Cl)-C(＝O)-O-(CH
2)
2-S-(CH
2)
2-Rf
CH
2＝C(-Cl)-C(＝O)-O-(CH
2)
2-SO
2-Rf
CH
2＝C(-Cl)-C(＝O)-O-(CH
2)
2-SO
2-(CH
2)
2-Rf
CH
2＝C(-Cl)-C(＝O)-NH-(CH
2)
2-Rf
CH
2＝C(-Cl)-C(＝O)-O-(CH
2)
3-S-Rf
(in the formula, Rf is that carbonatoms is 1～6 a straight chain shape or a chain fluoro-alkyl.)
Repeating unit (B-2) is to be derived by the monomer of contain fluorine atoms (b) not to obtain.That monomer (b) is preferably is not fluorine-containing, have the monomer of the two keys of carbon-carbon.Monomer (b) is preferably not fluorine-containing vinyl-type monomer.The monomer of contain fluorine atoms (b) generally is not the compound with the two keys of 1 carbon-carbon.As the preferred monomer of the institute of the monomer of contain fluorine atoms (b) not, for example, can example ethene, vinyl-acetic ester, vinyl halides (for example vinylchlorid), meta-halo ethylene (for example vinylidene chloride), vinyl cyanide, vinylbenzene, polyoxyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, vinyl alkyl ethers, isoprene etc., but be not limited to these compounds.Monomer (b) can be (methyl) acrylate monomer and (methyl) acrylate monomeric mixture in addition.(methyl) acrylate monomer can be for example 5: 95 to 95: 5 with (methyl) acrylate monomeric weight ratio in addition, especially can be 70: 30 to 30: 70.
The monomer of contain fluorine atoms (b) can not be (methyl) acrylate that contains alkyl.The carbonatoms of alkyl can be for 1～30, for example be 6～30, can be exemplified as 10～30.The monomer of contain fluorine atoms (b) for example can not be the esters of acrylic acid that following general formula is represented.
CH
2＝CA
1COOA
2
In the formula, A
1Be hydrogen atom or methyl, A
2Be C
nH
2n+1(n=1～30) expression alkyl or-(A
11-O)
p-A
12(wherein, A
11Be that carbonatoms is 2～5 alkyl, A
12Be that hydrogen atom or carbonatoms are 1～5 alkyl, p is 1～20) expression alkoxide group.
Repeating unit (B-3) is derived by cross-linkable monomer (c) and is obtained.Cross-linkable monomer (c) can be to have at least 2 reactive groups and/or two keys of carbon-carbon and not fluorine-containing compound.Cross-linkable monomer (c) can be the compound that has the compound of the two keys of at least 2 carbon-carbon or have the two keys of at least 1 carbon-carbon and at least 1 reactive group.The example of reactive group is hydroxyl, epoxy group(ing), chloromethyl, blocked isocyanate, amino, carbonyl etc.
As cross-linkable monomer (c), for example, but example diacetone-acryloamide(DAA), (methyl) acrylamide, N hydroxymethyl acrylamide, (methyl) vinylformic acid hydroxy methyl, (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid 3-chloro-2-hydroxy propyl ester, (methyl) vinylformic acid N, N-dimethylaminoethyl, (methyl) vinylformic acid N, N-lignocaine ethyl ester, divinyl, chloroprene, (methyl) glycidyl acrylate etc., but be not limited to these compounds.
By making monomer (b) and/or monomer (c) copolymerization, can improve the various character such as anti-spatter property, washing fastness, the solvability in solvent, hardness, sense of touch of water and oil-resistant and didirtresistance and these performances as required.
In fluoropolymer, fluorochemical monomer (a) with respect to 100 weight parts, the amount of the monomer of contain fluorine atoms (b) is not 0 weight part～200 weight parts, 0.1 weight part～100 weight parts, for example is 0.1 weight part～50 weight parts, the amount of cross-linkable monomer (c) be 0 weight part～50 weight parts, for example be 0 weight part～20 weight parts, especially can be 0.1 weight part～15 weight parts.
The weight-average molecular weight of polymkeric substance is measured by gel permeation chromatography (GPC), can be for 5000～2000000, for example be 10000～1000000.
Fluoropolymer can be made by following operation.
For solution polymerization, adopt following method: exist under the condition of polymerization starter, monomer be dissolved in the organic solvent, carry out nitrogen displacement after, heated and stirred is 1 hour～10 hours under 30 ℃～120 ℃ scope.As polymerization starter, can enumerate for example Diisopropyl azodicarboxylate, benzoyl peroxide, ditertiary butyl peroxide, lauryl peroxide, hydrogen phosphide cumene, the peroxidation trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate etc.With respect to the monomer of 100 weight parts, can use 0.01 weight part～20 weight parts, the polymerization starter of 0.01 weight part～10 weight parts for example.
Organic solvent is to be inertia but the monomeric material of solubilized to monomer, can enumerate for example acetone, chloroform, HCHC225, Virahol, pentane, hexane, heptane, octane, hexanaphthene, benzene,toluene,xylene, sherwood oil, tetrahydrofuran (THF), 1,4-diox, butanone, methyl iso-butyl ketone (MIBK), ethyl acetate, butylacetate, 1,1,2,2-tetrachloroethane, 1, trieline, zellon, difluoro tetrachloroethane, Freon 113 etc.With respect to the monomer total amount of 100 weight parts, can use 50 weight parts～2000 weight parts, the organic solvent of 50 weight parts～1000 weight parts for example.
For emulsion polymerization, adopt following method: under the condition that has polymerization starter and emulsifying agent, make monomer emulsification in water, carry out nitrogen displacement after, under 50 ℃～80 ℃ scope, stir and made its copolymerization in 1 hour～10 hours.As polymerization starter, can use water-soluble substanceses such as benzoyl peroxide, lauroyl peroxide, t-butylperoxyl benzoate, 1-hydroxy-cyclohexyl hydrogen peroxide, 3-carbonyl propionyl superoxide, acetyl peroxide, azo diisobutyl amidine-dihydrochloride, Diisopropyl azodicarboxylate, sodium peroxide, Potassium Persulphate, ammonium persulphate; Oil-soluble substances such as Diisopropyl azodicarboxylate, benzoyl peroxide, ditertiary butyl peroxide, lauryl peroxide, hydrogen phosphide cumene, the peroxidation trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate.With respect to the monomer of 100 weight parts, can use 0.01～10 weight part polymerization starter.
In order to obtain the multipolymer aqueous dispersions of shelf-stability excellence, preferably use high-pressure homogenizer, the such emulsifier unit that can give powerful pulverizing energy of ultrasonic homogenizer, in water, make monomer form particulate, use oil-soluble polymerization initiator to carry out polymerization.In addition,, the various emulsifying agents of anionic property, cationic or nonionic can be used,, 0.5 weight part～20 weight part emulsifying agents can be used with respect to the monomer of 100 weight parts as emulsifying agent.The preferred emulsifying agent that uses anionic property and/or nonionic and/or cationic.Monomer is complete when incompatible, preferably adds making its fully compatible compatilizer, for example water-miscible organic solvent or low-molecular-weight monomer in these monomers.By adding compatilizer, can improve emulsifying property and copolymerization.
As water-miscible organic solvent, can enumerate acetone, butanone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol etc., with respect to the water of 100 weight parts, can use 1 weight part～50 weight parts, the water-miscible organic solvent of 10 weight parts～40 weight parts for example.In addition, as low-molecular-weight monomer, can enumerate methyl methacrylate, glycidyl methacrylate, methacrylic acid 2,2,2-trifluoroethyl ester etc., with respect to the monomer total amount of 100 weight parts, water-miscible organic solvent can use 1 weight part～50 weight parts, 10 weight parts～40 weight parts for example.
The mixture that contains fluoropolymer (B) is preferably solution, emulsion or aerocolloidal form.Mixture contains fluoropolymer and medium (for example liquid medium of organic solvent and water etc.).In mixture, the concentration of fluoropolymer (B) can be for example 0.01 weight %～70 weight %.
Composition of the present invention can also contain silicon-containing compound (C).
The example of silicon-containing compound (C) is silicone oil, modified silicone and silicone resin.
The example of silicon-containing compound (C) is as follows.
Silicone oil
Compound group 14
(in the formula, n is 1～100000 integer.)
Modified silicone
Compound group 15
(in the formula, A is that directly combination or carbonatoms are 1～20 alkyl, and X is epoxy group(ing), amido, carbonyl, aryl or hydroxyl, and a and b are 1～100000 integer.)
Silicone resin
Compound group 16
(in the formula, R is aliphatic alkyl (for example methyl), aromatic hydrocarbyl (for example aryl), and n is 1～100000 integer.)
With respect to the total amount of 100 weight part fluorine-containing urethane compounds (A) and fluoropolymer (B), the amount of silicon-containing compound (C) can be for example 0 weight part～20 weight parts, particularly 1 weight part～5 weight parts.
Composition of the present invention is preferably solution, emulsion or aerocolloidal form.Composition generally contains liquid medium (for example organic solvent and water).Composition can also contain emulsifying agent (with respect to the total amount of 100 weight part fluorine-containing urethane (A) and fluoropolymer (B) and the silicon-containing compound (C) that adds as required, the amount of emulsifying agent is generally 0.5 weight part～30 weight parts).
Composition of the present invention can contain the mixture of fluorine-containing urethane compound (A) and liquid medium (for example organic solvent and water) and contain fluoropolymer (B) and the mixture of liquid medium (for example organic solvent and water) obtains by mixing.Before the mixing, can heat (for example 40 ℃～90 ℃ heating 1 minute～120 minutes) as required.When composition is emulsion, after the mixing, as required can be with mulser with composition emulsification and/or in composition, add emulsifying agent.In composition, fluorine-containing urethane (A) can be 95: 5 to 5: 95 with the weight ratio of fluoropolymer (B), especially can be 90: 10 to 30: 70, and then can be 85: 15 to 40: 60, and for example be 80: 20 to 50: 50.In composition, the total concn of fluorine-containing urethane (A) and fluoropolymer (B) and the silicon-containing compound (C) that adds as required can be for example 0.05 weight %～70 weight %.In liquid medium, the weight ratio of organic solvent and water can be 0: 100 to 100: 0, for example is 5: 95 to 95: 5.
Agent composition of the present invention can be applied to object being treated by known method in the past.Usually adopt following method: this treatment agent is dispersed in organic solvent or the water dilutes,, make treatment agent be attached to the object being treated surface, carry out drying then by known methods such as dip-coating, spraying, foaming coatings.In addition, in case of necessity, also can and be cured with suitable linking agent.And then, in treatment agent of the present invention, can also add other treatment agents (for example water-resisting agent or oil-proofing agent) or insect-proof agent, softening agent, antiseptic-germicide, fire retardant, antistatic agent, coating adhesive agent, anti-creasing agent waits together and uses.During dip-coating, the fluorine-containing urethane compound in the steeping fluid and the total concn of fluoropolymer can be 0.05 weight %～10 weight %.During spraying, the fluorine-containing urethane compound in the treatment solution and the total concn of fluoropolymer can be 0.1 weight %～5 weight %.Also can and use stain control agent (stain blocker).When using stain control agent, preferably use anionic property or non-ionic emulsifier.
As the object being treated of handling with agent composition of the present invention surface treatment agents such as (for example) water and oil repellent agents, can enumerate parts (for example gas diffusion electrode and gaseous diffusion upholder), glass, paper, wood, leather, fur, asbestos, brick, cement, metal and oxide compound, ceramic industry goods, plastics, coat side and the plaster etc. of fibre product (for example tilting blanket, non-woven fabrics), stone material, filter (for example static filter), dust respirator, fuel cell.Fibre product is tilting blanket particularly.As fibre product, can enumerate various examples.For example, of animal or plant nature natural fibers such as cotton, fiber crops, wool, silk; Synthon such as polymeric amide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, semi-synthetic fibres such as regenerated fiber, acetic ester, inorganic fibres such as glass fibre, carbon fiber, fire-retardant fibre, perhaps their blend fiber.Machining agent of the present invention is owing to lotion solution, brush (mechanical) being had excellent resistivity, so can perform well in nylon, polyacrylic tilting blanket.
Fibre product can be forms such as fiber, yarn, cloth.When handling tilting blanket, form tilting blanket after can handling fiber or yarn with surface treatment agent, perhaps also can handle established tilting blanket with surface treatment agent with surface treatment agent of the present invention.Fluorine-containing urethane compound (A) forms more uniform filming in the temperature that is lower than fibre product treatment temp (being generally 90 ℃～130 ℃) slightly (for example about 80 ℃～100 ℃) rapid fusion down on fibre product, thereby brings excellent didirtresistance.
Can handle (treatment process is the Exhaust method) to fibre product, its treatment process has following operation: the pH that (1) modulation contains treatment agent is the operation of the treatment solution below 7; (2) fibre product is used the operation of treatment solution; (3) fibre product is carried out the operation of steam treatment; (4) operation to dewatering after the fibre product washing.
Embodiment
Be specifically described for embodiments of the invention, but embodiment does not limit the present invention.
The water-repellancy experiment
In the constant temperature and humidity machine of 21 ℃ of temperature, humidity 65%, preserve more than 4 hours the tilting blanket after the treated dose of processing.Experiment liquid (Virahol (IPA), water and mixed solution thereof, as shown in table 1) also uses the experiment liquid after preserving under 21 ℃ the temperature.Experiment is carried out in the thermostatic constant wet chamber of 21 ℃ of temperature, humidity 65%.With micropipet(te) on tilting blanket at leisure Dropwise 5 drip (1 is 50 μ l) experiment liquid, placed for 10 seconds after, if drop on tilting blanket residual 4 or 5, it is qualified then to estimate this experiment liquid.As its mark, is that water-repellancy bad to good horizontal with failure, 0,1,2,3,4,5,6,7,8,9 and 10 these 12 grade evaluation water-repellancies with the maximum mark of Virahol (IPA) content (volume %) of qualified experiment liquid.
[table 1]
Table 1 water-repellancy experiment liquid
| (volume ratio %) | ||
| Mark | Virahol | Water |
| 10 | 100 | 0 |
| 9 | 90 | 10 |
| 8 | 80 | 20 |
| 7 | 70 | 30 |
| 6 | 60 | 40 |
| 5 | 50 | 50 |
| 4 | 40 | 60 |
| 3 | 30 | 70 |
| 2 | 20 | 80 |
| 1 | 10 | 90 |
| 0 | 0 | 100 |
| Failure | Do not reach Virahol: water is 0: 100 result | |
The grease proofness experiment
In the constant temperature and humidity machine of 21 ℃ of temperature, humidity 65%, preserve more than 4 hours the tilting blanket after the treated dose of processing.Experiment liquid (being shown in table 2) also uses the experiment liquid after preserving under 21 ℃ the temperature.Experiment is carried out in the thermostatic constant wet chamber of 21 ℃ of temperature, humidity 65%.With micropipet(te) on tilting blanket at leisure Dropwise 5 drip (1 is 50 μ l) experiment liquid, placed for 30 seconds after, if drop on tilting blanket residual 4 or 5, it is qualified then to estimate this experiment liquid.Highest score based on qualified experiment liquid is that grease proofness is bad to good horizontal with failure, 1,2,3,4,5,6,7 and 8 these 9 grade evaluation grease proofnesses.
[table 2]
Table 2 grease proofness experiment liquid
| Mark | Experiment liquid | Surface tension (dyne/cm, 25 ℃) |
| 8 | Normal heptane | 20.0 |
| 7 | Octane | 21.8 |
| 6 | N-decane | 23.5 |
| 5 | Positive 12 carbon alkane | 25.0 |
| 4 | N-tetradecane | 26.7 |
| 3 | Hexadecane | 27.3 |
| 2 | The mixed solution of hexadecane 35/ whiteruss 65 | 29.6 |
| 1 | Whiteruss (n-nujol) | 31.2 |
| Failure | Do not reach 1 result | - |
The didirtresistance experiment
Carry out according to AATCC Test Method 123-1989.
In didirtresistance is estimated, use that becoming fades use gray scale, compare with the tilting blanket sample before the didirtresistance experiment, with 1,1-2,2,2-3,3,3-4,4,4-5 and 5 these 9 grades significantly do not estimate to the level that has change to fade fully fading from change.
Synthesis example 1
Synthesizing of 3-(perfluor butylthio) propyl alcohol
With 34.6g (100mmol) 1,1,1,2,2,3,3,4,4-nine fluoro-4-butyl iodides are dissolved in dimethyl formamide (DMF) (100ml) and in the mixed solution of water (20ml), add 9.2g (100mmol) mercaprol then.Further add 6.8g (100mmol) sodium formiate, 25.2g (100mmol) S-WAT heptahydrate, at one night of stirring at room.
In reaction solution, add entry (250ml) and isopropyl ether (250ml), carry out separatory, further use isopropyl ether aqueous layer extracted (100ml * 2) afterwards, with 10% hydrochloric acid (125ml), water (125ml), saturated aqueous common salt (125ml) washing organic layer, then carry out drying, filter then, distill to remove and desolvate with anhydrous magnesium sulfate.Obtain 31.0g enriched material (3-(perfluor butylthio) propyl alcohol).Yield is 100%.
1H NMR (CDCl
3In be designated as TMS δ ppm): 3.78 (t, 2H, J
HH=5.9Hz, CH
2OH), 3.09 (t, 2H, J
HH=7.1Hz, SCH
2), 1.96 (tt, 2H, J
HH=7.1Hz, J
HH=5.9Hz, CH
2CH
2CH
2)
19F NMR (CDCl
3In be designated as CFCl
3δ ppm) :-81.5 (m, 3F, CF
3) ,-88.2 (m, 2F, CF
2S) ,-121.3 (m, 2F, CF
2) ,-126.0 (m, 2F, CF
2).
Synthesis example 2
Synthesizing of 3-(perfluoro butyl alkylsulfonyl) propyl alcohol
3-(perfluor butylthio) propyl alcohol that 8.60g (27.6mmol) is obtained in synthesis example 1 is dissolved in the 80ml methylene dichloride, calcium chloride tube is being installed and is carrying out under the stirring condition, at room temperature dividing 2 times and add 52g (232mmol) metachloroperbenzoic acid (m-CPBA).At room temperature stirred 7 days.Be injected in the mixture of 130g Sulfothiorine pentahydrate and 200ml water, stirred 1 hour.Add the 100ml methylene dichloride, isolate organic layer after, with 50ml dichloromethane extraction water layer.Merge organic layer,, carry out drying with sodium sulfate then with 5% sodium bicarbonate water, saturated common salt water washing.The concentrating under reduced pressure filtrate filtered, residue is carried out silica gel column chromatography, and (the expansion solvent is a hexane: ethyl acetate=2: 1) analyze, merge R
fValue is 0.32[R
fValue (tlc (TLC))=(movement of sample distance)/(launching the miles of relative movement of solvent)] cut, carry out concentrating under reduced pressure, obtain the crystalline 3-of 8.79g (perfluoro butyl alkylsulfonyl) propyl alcohol by vacuum-drying.Yield is 91.8%.
1H NMR (CDCl
3In be designated as TMS δ ppm): 3.85 (t, 2H, J
HH=5.8Hz, CH
2OH), 3.47 (t, 2H, J
HH=7.6Hz, SO
2CH
2), 2.22 (tt, 2H, J
HH=7.6Hz, J
HH=5.8Hz, CH
2CH
2CH
2)
19F NMR (CDCl
3In be designated as CFCl
3δ ppm) :-81.2 (m, 3F, CF
3) ,-113.8 (m, 2F, CF
2SO
2) ,-121.8 (m, 2F, CF
2) ,-126.3 (m, 2F, CF
2).
Production Example 1
1,3,5-three [6-{3-(perfluoro butyl alkylsulfonyl) propyl carbamate } hexyl]-1,3,5-triazines-2,4,6-triketone synthetic
(weight ratio of m=1,2,3 compound is 55: 20: 25 a mixture)
3-(perfluoro butyl alkylsulfonyl) propyl alcohol that 8.79g (25.7mmol) is obtained in synthesis example 2 is dissolved in the 27ml methyl iso-butyl ketone (MIBK) (MIBK); add 8mg (0.013mmol) dibutyl tin laurate; temperature is 72 ℃～75 ℃ in the adjusting reaction vessel under the condition of calcium chloride tube is installed, simultaneously with the ス ミ ジ ユ one Le N 3300 that dripped 4.95g (NCO equivalent 25.8mmol) in 1.5 hours and the solution of 9ml methyl iso-butyl ketone (MIBK).After being added dropwise to complete, stirred the concentrating under reduced pressure solvent 1 hour at 75 ℃.In residue, add hexane, leach the crystallization of separating out, carry out vacuum-drying, obtain 13.7g white powder crystallization (fluorine-containing urethane compound).Yield is 100%.
1H NMR (CD
3COCD
3In be designated as TMS δ ppm): 6.35 (wide unimodal, 3H, NHCO), 4.20 (t, 6H, J
HH=6.1Hz, CH
2O * 3), 3.84 (t, 6H, J
HH=7.3Hz, CH
2NHCO * 3), 3.70 (t, 6H, J
HH=7.8Hz, SO
2CH
2* 3), 3.12 (q, 6H, J
HH=6.6Hz, CH
2N (CO)
2* 3), 2.25 (tt, 6H, J
HH=7.8Hz, J
HH=6.1Hz, CH
2CH
2CH
2* 3), 1.56 (m * 2,12H, CH
2* 6), 1.36 (m, 12H, CH
2* 6)
19F NMR (CD
3COCD
3In be designated as CFCl
3δ ppm) :-80.6 (m, 9f, CF
3* 3) ,-113.2 (m, 6F, CF
2SO
2* 3) ,-121.0 (m, 6F, CF
2* 3) ,-125.6 (m, 6F, CF
2* 3).
Production Example 2
1,3,5-three { 6-(3,3,4,4,5,5,6,6,6-nine fluorine hexyl carbamates) hexyl }-1,3,5-triazines-2,4,6-triketone synthetic
With 26.4g (100mmol) perfluoro butyl dissolve with ethanol in 107ml methyl iso-butyl ketone (MIBK) (MIBK), add 32mg (0.051mmol) dibutyl tin laurate, temperature is 72 ℃～75 ℃ in the adjustment reaction vessel under the condition of calcium chloride tube is installed, simultaneously with the ス ミ ジ ユ one Le N 3300 that dripped 19.2g (NCO equivalent 100mmol) in 3.5 hours and the solution of 32ml methyl iso-butyl ketone (MIBK).After dripping off, stirred 2 hours at 75 ℃～76 ℃, concentrating under reduced pressure carries out vacuum-drying after removing and desolvating, and obtains 45.6g heavy-gravity troubled liquor.Yield is 100%.
1H NMR (CD
3COCD
3In be designated as TMS δ ppm): 6.38 (wide unimodal, 3H, NHCO), 4.33 (t, 6H, J
HH=6.2Hz, CH
2O * 3), 3.84 (t, 6H, J
HH=7.2Hz, CH
2NHCO * 3), 3.13 (q, 6H, J
HH=6.3Hz, CH
2N (CO) 2 * 3), 2.6 (m, 6H, CH
2CF
2* 3), 1.56 (m * 2,12H, CH
2* 6), 1.36 (m, 12H, CH
2* 6)
19F NMR (CD
3COCD
3In be designated as CFCl
3δ ppm) :-81.0 (m, 9F, CF
3* 3) ,-113.3 (m, 6F, CF
2* 3) ,-124.2 (m, 6F, CF
2* 3) ,-125.7 (m, 6F, CF
2* 3).
Production Example 3
The C that in 1 liter autoclave, adds 150g
4F
9CH
2CH
2OCOC (Cl)=CH
2, the methacrylic acid 3-chloro-2-hydroxy propyl ester of 19.4g vinylformic acid stearyl, 1.15g, the N hydroxymethyl acrylamide of 4.8g, 516g pure water, 62.97g tripropylene glycol, 1.14g acetate, the two hydrogenated tallow alkyl-dimethyl ammonium chlorides of 5.16g, 3.6g sorbitan monopalmitate, 3.6g polyoxyethylene oleyl ether, 11.1g polyoxyethylene polyoxypropylene cetyl ether, stirred 15 minutes at 60 ℃, its emulsification is disperseed with ultrasonic wave.Add the 11.5g n-dodecyl mercaptan after the emulsification, further be pressed into and fill 56.0g vinylchlorid.Further add 2 of 1.70g, two (2-amidine propane) dihydrochlorides of 2 '-azo make its reaction 5 hours at 60 ℃, obtain the water-based emulsion of polymkeric substance.In the composition of polymkeric substance, the reactivity of vinylchlorid is about 85%, and other monomeric reactivities are about 100%.Further in this water-based emulsion, add 3g polyoxyethylene sorbitan mono-laurate, stirred 1 hour, obtain aqueous liquid dispersion (polymer concentration: 30 weight %).
Production Example 4
The C that in 1 liter autoclave, adds 150g
4F
9CH
2CH
2OCOCH=CH
2, the methacrylic acid 3-chloro-2-hydroxy propyl ester of 19.4g vinylformic acid stearyl, 1.15g, the N hydroxymethyl acrylamide of 4.8g, 516g pure water, 62.97g tripropylene glycol, 1.14g acetate, the two hydrogenated tallow alkyl-dimethyl ammonium chlorides of 5.16g, 3.6g sorbitan monopalmitate, 3.6g polyoxyethylene oleyl ether, 11.1g polyoxyethylene polyoxypropylene cetyl ether, stirred 15 minutes at 60 ℃, its emulsification is disperseed with ultrasonic wave.Add the 11.5g n-dodecyl mercaptan after the emulsification, further be pressed into and fill 56.0g vinylchlorid.Further add 2 of 1.70g, two (2-amidine propane) dihydrochlorides of 2 '-azo make its reaction 5 hours at 60 ℃, obtain the water-based emulsion of polymkeric substance.In the composition of polymkeric substance, the reactivity of vinylchlorid is about 85%, and other monomeric reactivities are about 100%.Further in this water-based emulsion, add 3g polyoxyethylene sorbitan mono-laurate, stirred 1 hour, obtain aqueous liquid dispersion (polymer concentration: 30 weight %).
Embodiment 1
With 2g synthetic fluorine-containing urethane compound and 2g methyl iso-butyl ketone (MIBK) (MIBK) mixing in Production Example 1,75 ℃～80 ℃ heating 10 minutes.The alpha-olefin sodium sulfonate (anionic emulsifier) that mixes 15.6g pure water, 0.24g Voranol EP 2001 (non-ionic emulsifier) and 0.1g in other container was 75 ℃～80 ℃ heating 10 minutes.Mix this two kinds of liquid, carry out emulsification, obtain emulsion with the ultrasonic emulsification machine.
Add entry to this emulsion of 4.4g and 0.4g in by Production Example 3 synthetic emulsions, make total amount reach 100g, make treatment solution.((density is 26oz/yd for 20cm * 20cm, nylon 6, uncut pile to tilting blanket with this treatment solution
2)) processing of jetting, make WPU (wet pickup, be WPU30% when 30g liquid with respect to the 100g tilting blanket) amount reach 30%.Then, carry out thermofixation in 10 minutes at 120 ℃.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 3.
Embodiment 2
According to embodiment 1, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 1.Add entry to this emulsion of 3.6g and 0.6g in by Production Example 3 synthetic emulsions, make total amount reach 100g, make treatment solution.Utilize treatment agent that tilting blanket is handled according to embodiment 1.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 3.
Embodiment 3
According to embodiment 1, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 1.Add entry to this emulsion of 2.7g and 0.9g in by Production Example 3 synthetic emulsions, make total amount reach 100g, make treatment solution.Carrying out treatment agent according to 1 pair of tilting blanket of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 3.
Embodiment 4
With 2g synthetic fluorine-containing urethane compound and 2g methyl iso-butyl ketone (MIBK) (MIBK) mixing in Production Example 1,75 ℃～80 ℃ heating 10 minutes.The alpha-olefin sodium sulfonate (anionic emulsifier) that mixes 15.6g pure water, 0.24g Voranol EP 2001 (non-ionic emulsifier) and 0.1g in other container was 75 ℃～80 ℃ heating 10 minutes.Mix this two kinds of liquid, carry out emulsification with the ultrasonic emulsification machine.
Add 0.4g by Production Example 3 synthetic emulsions, 6g stain control agent A and water in this emulsion of 4.4g, being diluted to total amount is 1000g.Add the 10% thionamic acid aqueous solution, make its pH reach 1.5, obtain treatment solution.(20cm * 20cm, nylon 6, clipping, density are 32oz/yd to wring out the tilting blanket of WPU about 25% (WPU: wet pickup, be WPU25% during with 25g liquid with respect to the 100g tilting blanket) after will washing
2) in this treatment solution, flooded 30 seconds, wring out WPU (wet pickup) amount then and reach 300%.Fluorine concentration on the tilting blanket after the processing reaches 500ppm.Then, under the supine state of tilting blanket pile, carry out 90 seconds atmospheric steams and handle (temperature is 100 ℃～107 ℃).Then, after washing with 10 premium on currency, carry out centrifuge dehydration, make the WPU amount reach about 25%.At last, carry out thermofixation in 10 minutes at 110 ℃.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 4.
Embodiment 5
According to embodiment 4, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 1.Add 0.6g by Production Example 3 synthetic emulsions, 6g stain control agent A and water in this emulsion of 3.6g, being diluted to total amount is 1000g.Add the 10% thionamic acid aqueous solution again, make its pH reach 1.5, obtain treatment solution.According to embodiment 4, utilize this treatment solution that tilting blanket is handled.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 4.
Embodiment 6
According to embodiment 4, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 1.Add 0.9g by Production Example 3 synthetic emulsions, 6g stain control agent A and water in this emulsion of 2.7g, being diluted to total amount is 1000g.Add the 10% thionamic acid aqueous solution again, make its pH reach 1.5, obtain treatment solution.According to embodiment 4, utilize this treatment solution that tilting blanket is handled.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 4.
Embodiment 7
According to embodiment 1, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 2.Add entry to this emulsion of 4.7g and 0.4g in by Production Example 3 synthetic emulsions, make total amount reach 100g, make treatment solution.According to embodiment 1, utilize this treatment solution that tilting blanket is handled.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 5.
Embodiment 8
According to embodiment 1, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 2.Add entry to this emulsion of 3.8g and 0.6g in by Production Example 3 synthetic emulsions, make total amount reach 100g, make treatment solution.According to embodiment 1, utilize this treatment solution that tilting blanket is handled.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 5.
Embodiment 9
According to embodiment 1, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 2.Pass through to add 94.7g water in the Production Example 3 synthetic emulsions to this emulsion of 2.9g and 0.9g, make total amount reach 100g, make treatment solution.According to embodiment 1, utilize this treatment solution that tilting blanket is handled.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 5.
Embodiment 10
According to embodiment 4, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 2.Add 0.4g by Production Example 3 synthetic emulsions, 6g stain control agent A and water in this emulsion of 4.7g, being diluted to total amount is 1000g.Add the 10% thionamic acid aqueous solution, make its pH reach 1.5, obtain treatment solution.According to embodiment 4, utilize this treatment solution that tilting blanket is handled.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 6.
Embodiment 11
According to embodiment 4, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 2.Add 0.6g by Production Example 3 synthetic emulsions, 6g stain control agent A and water in this emulsion of 3.8g, being diluted to total amount is 1000g.Add the 10% thionamic acid aqueous solution, make its pH reach 1.5, obtain treatment solution.According to embodiment 4, utilize this treatment solution that tilting blanket is prevented the agent processing.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 6.
Embodiment 12
According to embodiment 4, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 2.Add 0.9g by Production Example 3 synthetic emulsions, 6g stain control agent A and water in this emulsion of 2.9g, being diluted to total amount is 1000g.Add the 10% thionamic acid aqueous solution, make its pH reach 1.5, obtain treatment solution.Carrying out treatment agent according to 4 pairs of tilting blankets of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 6.
Comparative example 1
According to embodiment 1, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 1.In this emulsion of 5.5g, add entry, make total amount reach 100g, make treatment solution.Carrying out treatment agent according to 1 pair of tilting blanket of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 3.
Comparative example 2
Add entry to 1.8g in by Production Example 3 synthetic emulsions and dilute, make total amount reach 100g.According to embodiment 1, tilting blanket is carried out treatment agent handle.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 3.
Comparative example 3
According to embodiment 1, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 1.Add entry to this emulsion of 4.4g and 0.3g in by Production Example 4 synthetic emulsions, make total amount reach 100g, make treatment solution.Carrying out treatment agent according to 1 pair of tilting blanket of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 3.
Comparative example 4
According to embodiment 1, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 1.Add entry to this emulsion of 3.6g and 0.6g in by Production Example 4 synthetic emulsions, make total amount reach 100g, make treatment solution.Carrying out treatment agent according to 1 pair of tilting blanket of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 3.
Comparative example 5
According to embodiment 1, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 1.Add entry to this emulsion of 2.7g and 0.8g in by Production Example 4 synthetic emulsions, make total amount reach 100g, make treatment solution.Carrying out treatment agent according to 1 pair of tilting blanket of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 3.
Comparative example 6
Add entry to 1.6g in by Production Example 4 synthetic emulsions and dilute, make total amount reach 100g.Carrying out treatment agent according to 1 pair of tilting blanket of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 3.
Comparative example 7
According to embodiment 4, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 1.In this emulsion of 5.5g and 5g stain control agent A, add entry and dilute, make total amount reach 1000g.Add the 10% thionamic acid aqueous solution, make its pH reach 1.5, obtain treatment solution.Carrying out treatment agent according to 4 pairs of tilting blankets of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 4.
Comparative example 8
Add entry to 1.8g in by Production Example 3 synthetic emulsions and 5g stain control agent A and dilute, make total amount reach 1000g.Add the 10% thionamic acid aqueous solution, make its pH reach 1.5, obtain treatment solution.Carrying out treatment agent according to 4 pairs of tilting blankets of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 4.
Comparative example 9
According to embodiment 4, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 1.Add entry to this emulsion of 4.4g, 0.3g in by Production Example 4 synthetic emulsions and 5g stain control agent A and dilute, make total amount reach 1000g.Add the 10% thionamic acid aqueous solution, make its pH reach 1.5, obtain treatment solution.Carrying out treatment agent according to 4 pairs of tilting blankets of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 4.
Comparative example 10
According to embodiment 4, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 1.Add entry to this emulsion of 3.6g, 0.6g in by Production Example 4 synthetic emulsions and 5g stain control agent A and dilute, make total amount reach 1000g.Add the 10% thionamic acid aqueous solution, make its pH reach 1.5, obtain treatment solution.Carrying out treatment agent according to 4 pairs of tilting blankets of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 4.
Comparative example 11
According to embodiment 4, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 1.Add entry to this emulsion of 2.7g, 0.9g in by Production Example 4 synthetic emulsions and 5g stain control agent A and dilute, make total amount reach 1000g.Add the 10% thionamic acid aqueous solution, make its pH reach 1.5, obtain treatment solution.Carrying out treatment agent according to 4 pairs of tilting blankets of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 4.
Comparative example 12
Add entry to 1.6g in by Production Example 4 synthetic emulsions and 5g stain control agent A and dilute, make total amount reach 1000g.Add the 10% thionamic acid aqueous solution, make its pH reach 1.5, obtain treatment solution.Carrying out treatment agent according to 4 pairs of tilting blankets of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 4.
Comparative example 13
According to embodiment 1, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 2.In this emulsion of 5.9g, add entry, make total amount reach 100g, make treatment solution.Carrying out treatment agent according to 1 pair of tilting blanket of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 5.
Comparative example 14
According to embodiment 1, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 2.Add entry to this emulsion of 4.7g and 0.3g in by Production Example 4 synthetic emulsions, make total amount reach 100g, make treatment solution.Carrying out treatment agent according to 1 pair of tilting blanket of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 5.
Comparative example 15
According to embodiment 1, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 2.Add entry to this emulsion of 3.8g and 0.6g in by Production Example 4 synthetic emulsions, make total amount reach 100g, make treatment solution.Carrying out treatment agent according to 1 pair of tilting blanket of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 5.
Comparative example 16
According to embodiment 1, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 2.Add entry to this emulsion of 2.9g and 0.8g in by Production Example 4 synthetic emulsions, make total amount reach 100g, make treatment solution.Carrying out treatment agent according to 1 pair of tilting blanket of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 5.
Comparative example 17
According to embodiment 4, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 2.In this emulsion of 5.9g and 5g stain control agent A, add entry and dilute, make total amount reach 1000g.Add the 10% thionamic acid aqueous solution, make its pH reach 1.5, obtain treatment solution.Carrying out treatment agent according to 4 pairs of tilting blankets of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 6.
Comparative example 18
According to embodiment 4, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 2.Add entry to this emulsion of 4.7g, 0.3g in by Production Example 4 synthetic emulsions and 5g stain control agent A and dilute, make total amount reach 1000g.Add the 10% thionamic acid aqueous solution, make its pH reach 1.5, obtain treatment solution.Carrying out treatment agent according to 4 pairs of tilting blankets of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 6.
Comparative example 19
According to embodiment 4, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 2.Add entry to this emulsion of 3.8g, 0.6g in by Production Example 4 synthetic emulsions and 5g stain control agent A and dilute, make total amount reach 1000g.Add the 10% thionamic acid aqueous solution again, make its pH reach 1.5, obtain treatment solution.Carrying out treatment agent according to 4 pairs of tilting blankets of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 6.
Comparative example 20
According to embodiment 4, obtain emulsion by synthetic fluorine-containing urethane compound in Production Example 2.Add entry to this emulsion of 2.9g, 0.8g in by Production Example 4 synthetic emulsions and 5g stain control agent A and dilute, make total amount reach 1000g.Add the 10% thionamic acid aqueous solution, make its pH reach 1.5, obtain treatment solution.Carrying out treatment agent according to 4 pairs of tilting blankets of embodiment handles.
Then, carry out water-repellancy experiment, grease proofness experiment, didirtresistance experiment.The results are shown in the table 6.
[table 3]
Table 3
| Water-repellancy | Grease proofness | Didirtresistance | |
| Comparative example 1 | 2 | 2 | 5 |
| Embodiment 1 | 3 | 3 | 5 |
| Embodiment 2 | 3 | 3 | 5 |
| Embodiment 3 | 3 | 3 | 4 |
| Comparative example 2 | 3 | 3 | 2 |
| Comparative example 3 | 2 | 1 | 5 |
| Comparative example 4 | 2 | 1 | 5 |
| Comparative example 5 | 2 | 1 | 4 |
| Comparative example 6 | 2 | 1 | 1 |
[table 4]
Table 4
| Water-repellancy | Grease proofness | Didirtresistance | |
| Comparative example 7 | 2 | 2 | 5 |
| Embodiment 4 | 3 | 3 | 5 |
| Embodiment 5 | 3 | 3 | 5 |
| Embodiment 6 | 3 | 2 | 4 |
| Comparative example 8 | 3 | 3 | 2 |
| Comparative example 9 | 2 | 1 | 5 |
| Comparative example 10 | 2 | 1 | 5 |
| Comparative example 11 | 2 | 1 | 4 |
| Comparative example 12 | 2 | 1 | 1 |
[table 5]
Table 5
| Water-repellancy | Grease proofness | Didirtresistance | |
| Comparative example 13 | Failure | Failure | 3 |
| Embodiment 7 | 3 | 3 | 3 |
| Embodiment 8 | 3 | 3 | 3 |
| Embodiment 9 | 2 | 2 | 3 |
| Comparative example 2 | 3 | 3 | 2 |
| Comparative example 14 | 2 | 1 | 3 |
| Comparative example 15 | 2 | 1 | 2 |
| Comparative example 16 | 2 | 1 | 2 |
| Comparative example 6 | 2 | 1 | 1 |
[table 6]
Table 6
| Water-repellancy | Grease proofness | Didirtresistance | |
| Comparative example 17 | 1 | 1 | 3 |
| Embodiment 10 | 3 | 3 | 3 |
| Embodiment 11 | 3 | 3 | 3 |
| Embodiment 12 | 2 | 2 | 3 |
| Comparative example 8 | 3 | 3 | 2 |
| Comparative example 18 | 2 | 1 | 3 |
| Comparative example 19 | 2 | 1 | 2 |
| Comparative example 20 | 2 | 1 | 2 |
| Comparative example 12 | 2 | 1 | 1 |
The possibility of utilizing on the industry
Agent composition of the present invention can be used as various base materials are carried out surface-treated surface conditioning agent (for example water and oil repellent agent or antifouling agent).
Claims (29)
1, a kind of composition, it contains (A) and (B),
(A) fluorine-containing urethane compound;
(B) have fluoropolymer by the fluorochemical monomer institute repeat units derived of formula (I) expression,
CH
2＝C(-X)-C(＝O)-A-Rf (I)
In the formula (I), X is fluorine atom, chlorine atom, bromine atoms, iodine atom, CFX
1X
2Group, cyano group, carbonatoms be a straight chain shape of 1～20 or a chain fluoro-alkyl, replace or do not have the benzyl of replacement, replace or do not have the phenyl of replacement, wherein, and CFX
1X
2X in the group
1And X
2Be hydrogen atom, fluorine atom or chlorine atom;
A is-O-Y
1-or-Y
2-[(CH
2)
m-Z-]
p-(CH
2)
n-, wherein, Y
1Be carbonatoms be 1～10 aliphatic group, carbonatoms be 6～10 aromatic group or cyclic aliphatic group ,-CH
2CH
2N (R
1) SO
2-(CH
2CH
2)
a-group or-CH
2CH (OR
11) CH
2-group, R wherein
1Be that carbonatoms is 1～4 alkyl, a is 0 or 1, R
11Be hydrogen atom or ethanoyl; Y
2For-O-or-NH-, Z is-S-or-SO
2-, m is 1～10, and n is 0～10, and p is 0 or 1;
Rf is that carbonatoms is 1～6 a straight chain shape or a chain perfluoroalkyl.
2, composition as claimed in claim 1, wherein, the compound that fluorine-containing urethane compound (A) is represented for following formula,
Rf’-O-(C＝O)-NH)
aI(NH-(C＝O)-O-R’)
b
In the formula, each Rf ' is identical or different, is any monovalent organic radical group of containing at least 1 fluorine atom;
I be from isocyanate compound, remove all isocyanate group with (a+b) individual isocyanate group and the organic group of (a+b) valency;
Each R ' is identical or different, is any monovalent organic radical group of not contain fluorine atoms;
A is 1～15 integer, and b is 0～14 integer, and the summation of a and b is 1～15 integer.
3, composition as claimed in claim 1, wherein, fluorine-containing urethane compound (A) is the compound of formula (1) expression,
[Rf-A
1-Z-X
1-OC(＝O)NH-]
mI[-NHC(＝O)O-Y
1]
n[-NHC(＝O)O-((ClCH
2-)X
2O)
a-R
1]
k (1)
In the formula, I be from polyisocyanate compounds, remove isocyanate group and group;
Rf is that carbonatoms is 1～6 perfluoroalkyl;
A
1Be that directly combination or carbonatoms are 1～21 divalent organic group;
Z be direct combination ,-S-or-SO
2-;
X
1Be that direct combination or the carbonatoms that has at least 1 hydroxyl or do not have a hydroxyl are 1～5 a straight chain shape or a chain divalent aliphatic group;
X
2Be that carbonatoms is 2～5 a straight chain shape or chain 3 a valency aliphatic group;
Y
1It is the 1 valency organic group that has hydroxyl or do not have hydroxyl;
R
1Be that hydrogen atom or carbonatoms are 1～10 alkyl;
A is 1～20 number;
M is 1～15 number;
N and k are 0～14 numbers;
The summation of m and n and k is 2～15 number.
4, composition as claimed in claim 1, wherein, in fluorine-containing urethane compound (A), the polyisocyanate compounds that constitutes the I group is the derivative of fatty family polymeric polyisocyanate, fragrant family polymeric polyisocyanate, these polymeric polyisocyanates.
5, composition as claimed in claim 1, wherein, in fluorine-containing urethane compound (A), the polyisocyanate compounds that constitutes the I group is the isocyanic ester of vulcabond, polymeric diphenylmethanediisocyanate, modification.
6, composition as claimed in claim 3, wherein, in fluorine-containing urethane compound (A), A
1Group is a formula :-(CH
2)
p-,-CONR
11-R
12-,-CH
2C (OH) HCH
2-,-CH
2C (OCOR
13) HCH
2-or-O-Ar-CH
2-, in these chemical formulas, R
11Be that hydrogen or carbonatoms are 1～10 alkyl, R
12Be that carbonatoms is 1～10 alkylidene group, R
13Be hydrogen or methyl, Ar is that to have substituting group or do not have substituent carbonatoms for example be 6～20 arylidene, and p is 1～10 integer.
7, composition as claimed in claim 3, wherein, in fluorine-containing urethane compound (A), X
1Group is (i) or (ii),
(i) be to be selected from by-CH
2-,-CH
2CH
2-,-CH
2CH
2CH
2-,-CH
2CH
2CH
2CH
2-,-CH
2CH
2CH
2CH
2CH
2-,-C (CH
3) H-,-C (CH
3) H-CH
2-,-CH
2-C (CH
3) H-,-CH
2-C (CH
3) H-CH
2-,-C (CH
3) H-CH
2-CH
2-,-C (CH
3) H-C (CH
3) H-,-CH
2-C (CH
3)
2-CH
2-,-C (CH
3) H-C (CH
3) H-CH
2-and-C (CH
3) H-CH
2-C (CH
3) alkylidene group in the group formed of H-;
(ii) be selected from by-C (OH) H-,-C (OH) HCH
2-,-CH
2C (OH) H-,-C (OH) HC (OH) H-,-C (OH) HCH
2CH
2-,-CH
2C (OH) HCH
2-,-CH
2CH
2C (OH) H-,-C (OH) HC (OH) HCH
2-,-C (OH) HCH
2C (OH) H-,-CH
2C (OH) HC (OH) H-,-CH
2C (OH)
2CH
2-and-alkylidene group in the group that C (OH) HC (OH) HC (OH) H-forms with hydroxyl.
8, composition as claimed in claim 1, wherein, fluorine-containing urethane compound (A) formula (2) expression,
[Rf-A
1-Z-X
1-OC(＝O)NH-]
mI[-NHC(＝O)O-Y
1]
n (2)
In the formula, I removes isocyanate group and the group that obtains from polyisocyanate compounds;
Rf is that carbonatoms is 1～6 perfluoroalkyl;
A
1Be that directly combination or carbonatoms are 1～21 divalent organic group;
Z be direct combination ,-S-or-SO
2-;
X
1Be that direct combination or the carbonatoms that has at least 1 hydroxyl or do not have a hydroxyl are 1～5 a straight chain shape or a chain divalent aliphatic group;
Y
1It is the 1 valency organic group that has hydroxyl or do not have hydroxyl;
M is 1～15 number;
N is 0～14 number;
The summation of m and n is 2～15 number.
9, composition as claimed in claim 1, wherein, fluorine-containing urethane compound (A) formula (3) expression,
[Rf-A
1-Z-X
1-OC(＝O)NH-]
mI (3)
In the formula, I removes isocyanate group and the group that obtains from polyisocyanate compounds;
Rf is that carbonatoms is 1～6 perfluoroalkyl;
A
1Be that directly combination or carbonatoms are 1～21 divalent organic group;
Z be direct combination ,-S-or-SO
2-;
X
1Be that direct combination or the carbonatoms that has at least 1 hydroxyl or do not have a hydroxyl are 1～5 a straight chain shape or a chain divalent aliphatic group;
M is 2～15 number.
10, composition as claimed in claim 3, wherein, in fluorine-containing urethane compound (A), Y
1Be the compound that following formula is represented,
H-(O)
s-(CH
2)
t-
In the formula, s is 0 or 1, and t is 1～5 number,
Perhaps Y
1Be the compound of representing with following formula,
-(A
11-O)
p-A
12
In the formula, A
11Be that carbonatoms is 2～5 alkyl, A
12Be that hydrogen atom or carbonatoms are 1～5 alkyl, p is 0～20.
11, composition as claimed in claim 1, wherein, fluoropolymer (B) has repeating unit (B-1), (B-2) and (B-3),
(B-1) the fluorochemical monomer institute repeat units derived of representing by formula (I),
CH
2＝C(-X)-C(＝O)-A-Rf (I)
In the formula, X is fluorine atom, chlorine atom, bromine atoms, iodine atom, CFX
1X
2Group, cyano group, carbonatoms be a straight chain shape of 1～20 or a chain fluoro-alkyl, replace or do not have the benzyl of replacement, replace or do not have the phenyl of replacement, wherein, and CFX
1X
2X in the group
1And X
2Be hydrogen atom, fluorine atom or chlorine atom;
A is-O-Y
1-or-Y
2-[(CH
2)
m-Z-]
p-(CH
2)
n-, at this, Y
1Be carbonatoms be 1～10 aliphatic group, carbonatoms be 6～10 aromatic group or cyclic aliphatic group ,-CH
2CH
2N (R
1) SO
2-(CH
2CH
2)
a-group or-CH
2CH (OR
11) CH
2-group, wherein, R
1Be that hydrogen or carbonatoms are 1～4 alkyl, a is 0 or 1; R
11Be hydrogen atom or ethanoyl; Y
2For-O-or-NH-, Z is-S-or-SO
2-, m is 1～10, and n is 0～10, and p is 0 or 1;
Rf is that carbonatoms is 1～6 a straight chain shape or a chain perfluoroalkyl;
(B-2) by the monomer institute repeat units derived of contain fluorine atoms not;
(B-3) exist as required, by cross-linkable monomer institute repeat units derived.
12, composition as claimed in claim 11, wherein, in repeating unit (B-1), the carbonatoms of Rf group is 1～4.
13, composition as claimed in claim 11, wherein, the monomer that forms the not contain fluorine atoms of repeating unit (B-2) is the not fluorinated acrylate that following general formula is represented,
CH
2＝CA
1COOA
2
In the formula, A
1Be hydrogen atom or methyl, A
2Be that the carbonatoms that has Sauerstoffatom or do not have a Sauerstoffatom is 1～30 alkyl.
14, composition as claimed in claim 13, wherein, the A in the repeating unit (B-2)
2Group is C
nH
2n+1The expression alkyl or-(A
11-O)
p-A
12The alkoxide group of expression, in the above-mentioned formula, n=1～30, A
11Be that carbonatoms is 2～5 alkyl, A
12Be that hydrogen atom or carbonatoms are 1～5 alkyl, p is 1～20.
15, composition as claimed in claim 11, wherein, the cross-linkable monomer that forms repeating unit (B-3) is to have at least 2 reactive groups and/or carbon-to-carbon double bond and not fluorine-containing monomer.
16, composition as claimed in claim 11, wherein, in fluoropolymer (B), with respect to the fluorochemical monomer of 100 weight parts, the monomeric amount of contain fluorine atoms is not 0.1～50 weight part, the amount of cross-linkable monomer is below 20 weight parts.
17, composition as claimed in claim 1, wherein, the weight ratio of fluorine-containing urethane (A) and fluoropolymer (B) is 5: 95 to 95: 5.
18, composition as claimed in claim 1, wherein, fluorine-containing urethane (A) and fluoropolymer (B) have one of at least an alkylidene oxide, the alkylidene group in this alkylidene oxide has 2～5 carbon atoms, particularly has 2 or 3 carbon atoms.
19, composition as claimed in claim 1 wherein, also contains silicon-containing compound (C).
20, composition as claimed in claim 18, wherein, silicon-containing compound (C) is at least a kind of compound that is selected from the group of being made up of the silicone and the silicone resin of silicone oil, modification.
21, composition as claimed in claim 1, it is solution, emulsion or aerocolloidal form.
22, composition as claimed in claim 1 wherein, further contains emulsifying agent and water.
23, composition as claimed in claim 1, it is a surface treatment agent.
24, composition as claimed in claim 1, it is water and oil repellent agent or antifouling agent.
25, a kind of method wherein, is carried out surface treatment with the described composition of claim 1 to object being treated.
26, method as claimed in claim 25, wherein, object being treated be fibre product, stone material, for example static filter filter, dust respirator, fuel cell, glass, paper, wood, leather, fur, asbestos, brick, cement, metal and oxide compound, ceramic industry goods, plastics, be coated with face or plaster.
27, method as claimed in claim 25 wherein, has the processing of following operation to fibre product:
(1) modulating the pH that contains the described composition of claim 1 is the operation of the treatment solution below 7,
(2) fibre product is used the operation of treatment solution,
(3) to fibre product carry out steam treatment operation and
(4) operation to dewatering after the fibre product washing.
28, a kind of fibre product, it is handled with the described composition of claim 1 and obtains.
29, a kind of tilting blanket, it is handled with the described composition of claim 1 and obtains.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP316045/2004 | 2004-10-29 | ||
| JP2004316045 | 2004-10-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101065443A true CN101065443A (en) | 2007-10-31 |
Family
ID=36227885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800371778A Pending CN101065443A (en) | 2004-10-29 | 2005-10-27 | Fluorine-containing treatment composition |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US8197590B2 (en) |
| JP (1) | JPWO2006046643A1 (en) |
| CN (1) | CN101065443A (en) |
| WO (1) | WO2006046643A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265854A (en) * | 2013-05-24 | 2013-08-28 | 苏州市德莱尔建材科技有限公司 | Ethylene perchloride waterproof paint for wood material |
| CN104592847A (en) * | 2007-12-28 | 2015-05-06 | 大金工业株式会社 | Aqueous coating agent for electronic component and manufacturing method of processing electronic component |
| CN101981070B (en) * | 2008-03-28 | 2016-04-06 | 大金工业株式会社 | Fluoropolymer and water and oil repellent agent |
| CN105576087A (en) * | 2015-12-23 | 2016-05-11 | 广东威创视讯科技股份有限公司 | Surface treatment process and system of LED product |
| CN115819665A (en) * | 2022-12-28 | 2023-03-21 | 浙江辉凯鼎瑞新材料有限公司 | Fluorine-containing treating agent, preparation method thereof and application thereof to non-woven fabric |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1772552A3 (en) * | 2006-07-20 | 2007-06-20 | Singtex Industrial Co., Ltd. | Porous polytetrafluoroethylene membrane treated with an anti-staining and anti-peeling agent |
| US7470745B2 (en) | 2006-11-13 | 2008-12-30 | E. I. Du Pont De Nemours And Company | Perfluoroether based polymers |
| US8048953B2 (en) | 2006-11-13 | 2011-11-01 | E. I. Du Pont De Nemours And Company | Fluororpolymer compositions and treated substrates |
| US20080124555A1 (en) * | 2006-11-29 | 2008-05-29 | 3M Innovative Properties Company | Polymerizable composition comprising perfluoropolyether urethane having ethylene oxide repeat units |
| AU2008252105B2 (en) * | 2007-05-15 | 2011-05-19 | Daikin Industries, Ltd. | Water-repellent oil-repellent antifouling agent having good solubility in solvent |
| CN102918131B (en) * | 2010-06-04 | 2015-08-19 | 旭硝子株式会社 | Water-repellent oil-repellent agent and water-repellent oil-repellent agent composition |
| IN2013MU02827A (en) * | 2013-08-29 | 2015-07-03 | Green Impact Holdings Gmbh | |
| EP3356475A1 (en) * | 2015-10-02 | 2018-08-08 | The Chemours Company FC, LLC | Hydrophobic compound extenders in surface effect coatings |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3663604A (en) * | 1969-03-05 | 1972-05-16 | Fmc Corp | Polyfluorocarbamates |
| JPS6399285A (en) | 1986-05-28 | 1988-04-30 | Daikin Ind Ltd | Water and oil repellent |
| EP0247489B1 (en) | 1986-05-28 | 1993-08-25 | Daikin Industries, Limited | Fluorine containing water and oil repellent composition |
| JPS63146976A (en) | 1986-12-11 | 1988-06-18 | Daikin Ind Ltd | Water and oil repellent composition |
| DE4040641A1 (en) | 1990-12-19 | 1992-06-25 | Pfersee Chem Fab | AGENT FOR TREATING FIBER MATERIALS |
| JP3194394B2 (en) | 1992-03-18 | 2001-07-30 | 大日本インキ化学工業株式会社 | Method for producing polyurethane resin |
| JP3482710B2 (en) | 1994-10-27 | 2004-01-06 | 大日本インキ化学工業株式会社 | Method for producing aqueous fluororesin dispersion |
| WO1996030584A1 (en) | 1995-03-31 | 1996-10-03 | Minnesota Mining And Manufacturing Company | Aqueous oil and water repellent compositions |
| JPH08283654A (en) | 1995-04-19 | 1996-10-29 | Dainippon Ink & Chem Inc | Formation of stain-resistant coating membrane |
| JP4270360B2 (en) * | 2000-03-07 | 2009-05-27 | 大日精化工業株式会社 | Method for producing fluorine-containing diol, use of fluorine-containing diol |
| TW518319B (en) * | 2000-03-07 | 2003-01-21 | Dainichiseika Color & Amp Chem | Fluorine-containing diols and use thereof |
| JP2002363244A (en) | 2001-06-08 | 2002-12-18 | Toyo Tire & Rubber Co Ltd | Fluorine-containing polyurethane for coating material |
| US7078454B2 (en) | 2002-04-17 | 2006-07-18 | 3M Innovative Properties Company | Repellent fluorochemical compositions |
| JPWO2004013089A1 (en) * | 2002-08-06 | 2006-09-21 | ダイキン工業株式会社 | Fluorine-containing urethane compound and composition thereof |
| WO2005092937A1 (en) | 2004-03-26 | 2005-10-06 | Daikin Industries, Ltd. | Fluorine-containing monomer, fluorine-containing polymer and surface treating agent |
-
2005
- 2005-10-27 CN CNA2005800371778A patent/CN101065443A/en active Pending
- 2005-10-27 US US11/666,428 patent/US8197590B2/en not_active Expired - Fee Related
- 2005-10-27 JP JP2006543247A patent/JPWO2006046643A1/en not_active Withdrawn
- 2005-10-27 WO PCT/JP2005/019786 patent/WO2006046643A1/en not_active Application Discontinuation
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|---|---|---|---|---|
| CN104592847A (en) * | 2007-12-28 | 2015-05-06 | 大金工业株式会社 | Aqueous coating agent for electronic component and manufacturing method of processing electronic component |
| CN104592847B (en) * | 2007-12-28 | 2019-07-23 | 大金工业株式会社 | The manufacturing method of electronic component-use aqueous coating agent and processing electronic component |
| CN101981070B (en) * | 2008-03-28 | 2016-04-06 | 大金工业株式会社 | Fluoropolymer and water and oil repellent agent |
| CN103265854A (en) * | 2013-05-24 | 2013-08-28 | 苏州市德莱尔建材科技有限公司 | Ethylene perchloride waterproof paint for wood material |
| CN103265854B (en) * | 2013-05-24 | 2015-06-03 | 苏州市德莱尔建材科技有限公司 | Ethylene perchloride waterproof paint for wood material |
| CN105576087A (en) * | 2015-12-23 | 2016-05-11 | 广东威创视讯科技股份有限公司 | Surface treatment process and system of LED product |
| CN115819665A (en) * | 2022-12-28 | 2023-03-21 | 浙江辉凯鼎瑞新材料有限公司 | Fluorine-containing treating agent, preparation method thereof and application thereof to non-woven fabric |
| CN115819665B (en) * | 2022-12-28 | 2023-07-04 | 浙江辉凯鼎瑞新材料有限公司 | Fluorine-containing treating agent, preparation method thereof and application of fluorine-containing treating agent to non-woven fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| US20070295245A1 (en) | 2007-12-27 |
| US8197590B2 (en) | 2012-06-12 |
| JPWO2006046643A1 (en) | 2008-05-22 |
| WO2006046643A1 (en) | 2006-05-04 |
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